KR101718979B1 - A method for producing the fuel electrode side diffusion barrier layer of a metal-supported solid oxide fuel cell - Google Patents

Abstract

The present invention relates to a method for manufacturing a metal support solid oxide fuel cell capable of forming a porous anode diffusion preventing layer made of a conductive oxide, which has excellent bonding strength with a metal support by a normal temperature coating process without a high temperature heat treatment process to provide.
A method of manufacturing a cell for a metal-supported solid oxide fuel cell according to the present invention comprises the steps of: i) preparing the metal support; Ii) forming the anode diffusion preventing layer on one side of the metal support; Iii) forming the anode layer on the anode diffusion preventing layer; Iv) forming the solid electrolyte layer on the anode layer; (V) forming an air electrode interface reaction preventing layer selectively on the solid electrolyte layer; And (vi) forming the air electrode layer on the solid electrolyte layer or the air electrode interface reaction preventing layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a fuel electrode diffusion barrier layer of a metal support type solid oxide fuel cell,

The present invention relates to a metal-supported solid oxide fuel cell, and more particularly, to a method for manufacturing an anode diffusion preventive layer at room temperature in a unit cell of a metal-supported solid oxide fuel cell.

A solid oxide fuel cell (SOFC) has a structure in which a plurality of electricity generating units each comprising a unit cell and a separator plate are stacked. The unit cell includes a solid electrolyte layer, a fuel electrode (cathode) located on one side of the solid electrolyte layer, and an air electrode (anode) located on the other side of the solid electrolyte layer (membrane).

When oxygen is supplied to the air electrode and hydrogen is supplied to the fuel electrode, oxygen ions generated by the reduction reaction of oxygen in the air electrode travel through the solid electrolyte layer to the fuel electrode, and then water reacts with hydrogen supplied to the fuel electrode. At this time, the electrons generated in the anode are transferred to the cathode and consumed, and electrons flow to the external circuit, and the unit cell generates electric energy using the electron flow.

Therefore, the solid electrolyte layer is formed of a dense ion conductive layer which can not directly pass through the gas, and the air electrode and the fuel electrode should exhibit a porous structure that facilitates gas permeation and mixed conduction (electron and ion conductivity).

As the solid oxide fuel cell, there are an electrolyte support-type cell (ESC) type and an air electrode support type cell type or an anode support type cell type.

The electrolyte support type cell type (ESC) is composed of a thick electrolyte layer serving as a mechanical support, a thin anode layer and a cathode layer.

In the case of the electrolyte support type cell, when the solid electrolyte having a thickness of 100 to 500 μm required for the mechanical support is used, the Ohmic resistance of the solid electrolyte is large. Therefore, in order to obtain a certain level of single cell performance, Of high temperature.

In this case, expensive expensive heat-resistant and oxidation-resistant materials must be used for the stack and peripheral equipment (balance-of-plant, BOP).

The anode support cell can reduce the temperature of the SOFC operating temperature to less than 800 ° C. by reducing the ohmic of the electrolyte by forming a thin solid electrolyte layer of 5 to 20 μm thickness on the anode layer of 0.3 to 1000 μm thickness Although economical efficiency is improved, reliability of the SOFC stack can be secured only if the brittle fracture problem unique to ceramics is overcome.

On the other hand, since the metal support cell (MSC) uses a metal as a support, it is not only inexpensive to manufacture a cell, but also has excellent strength and flexibility.

Therefore, since the metal support type cells are resistant to thermal and mechanical shock and can perform rapid thermal cycling, the solid oxide fuel cell can be commercialized by greatly improving thermal mechanical reliability, which is a weak point of conventional SOFC stacks and systems.

Ferritic stainless steels are useful as such metal support type metals. Ferritic stainless steels are similar in thermal expansion coefficient to those of fuel electrodes, air electrodes and solid electrolytes, and have excellent oxidation resistance and are very economical compared to nickel or nickel alloys.

However, such ferritic stainless steels contain iron and chromium as main components, and these components cause a mutual diffusion reaction with the nickel component of the fuel electrode stacked on the metal support, thereby deteriorating the performance of the fuel cell.

That is, when the nickel component of the anode is diffused into the metal support formed of ferritic stainless steel, the surface of the metal support is transformed into the austenitic system by the diffusion of nickel. When the crystal phase of the stainless steel is changed, the intrinsic thermal expansion coefficient of the ferritic stainless steel material is greatly increased. There is a problem that the anode layer and the solid electrolyte layer, which are similar to the thermal expansion coefficient of the ferritic stainless steel, are peeled off.

Also, when iron and chromium, which are components of the ferritic stainless steel, diffuse from the metal support into the fuel electrode layer, the electrochemical activity of the fuel electrode layer decreases and the performance of the fuel cell decreases.

The interface reaction occurring between the metal support and the anode layer may occur during the process of manufacturing the fuel cell and during the operation of the cell. Therefore, if the operating temperature of the solid oxide fuel cell is lowered, the interfacial reaction can be suppressed. However, when the fuel cell is operated at such a low temperature, the performance of the fuel cell is deteriorated.

An excellent metal support body having a porous structure capable of passing fuel gas required for an electrochemical reaction and having an excellent bonding force with a metal support by a room temperature coating process without a high temperature heat treatment process and at the same time being made of a conductive oxide, A method of manufacturing a cell of an oxide fuel cell is provided.

The present invention provides a cell and a stack of a metal-supported solid oxide fuel cell which is manufactured by a normal-temperature coating process without high-temperature sintering and has excellent bonding force and electrochemical performance.

In one embodiment of the present invention, there is provided a method of manufacturing a cell for a metal-supported solid oxide fuel cell comprising a metal support, an anode layer, a solid electrolyte layer and a cathode layer, the anode diffusion preventive layer being disposed between the metal support and the anode layer, At a room temperature without forming a metal-supported solid oxide fuel cell.

The method for manufacturing a cell for a metal-supported solid oxide fuel cell includes the steps of: i) preparing the metal support; Ii) forming the anode diffusion preventing layer on one side of the metal support; Iii) forming the anode layer on the anode diffusion preventing layer; Iv) forming the solid electrolyte layer on the anode layer; (V) forming an air electrode interface reaction preventing layer selectively on the solid electrolyte layer; And (vi) forming the air electrode layer on the solid electrolyte layer or the air electrode interface reaction preventing layer.

At this time, the step of forming the anode diffusion preventing layer, the anode layer, the solid electrolyte layer and the air electrode interface reaction preventing layer may be formed by an aerosol spraying method. The forming of the cathode layer may be performed by a screen printing method or a spray painting method.

Here, the method of forming the anode diffusion preventing layer by the aerosol spraying method is as follows.

First, the conductive oxide powder and the pore-forming powder are heat-treated and pulverized, and the powders are prepared by controlling the particle size. Then, the powders are mixed to prepare a mixed powder. The mixed powder is mechanically vibrated, The aerosol is sprayed at high speed onto a metal support in a vacuum state to form an anode diffusion preventing layer by kinetic energy of the mixed powder.

Wherein the conductive oxide powder is at least one selected from the group consisting of CeO ₂ , (La _1-x A _x ) Cr _{1 -y} B _y O _{3 ± δ} (A = Sr, Ca or a mixture thereof x = 0.1 to 0.4; (A _1-x A _x ) _s Ti _1-y B _y O _{3 隆} (A, A, B, C, = Sr, Ca or a mixture thereof x = 0.1 to 0.6; B = Mn, Co, Cu, Ni, V, Fe, Ti, Ce, Ru or a mixture thereof y = 0 to 0.5; s = = 0 to 0.3), (Sr _1-x A _x ) _s Ti _1-y Nb _y O _{3 隆} (A = Y, La, Gd, Sm or a mixture thereof, x = 0.05-0.2; y = ; s = 0.9 to 1.0,? = 0 to 0.3).

In the heat treatment of the conductive oxide powder, the heat treatment of the conductive oxide powder is performed at 300 to 1200 ° C, preferably 600 to 1100 ° C, more preferably 800 to 1100 ° C, and further preferably 900 to 1000 ° C. will be.

On the other hand, the pore-forming precursor powder is preferably a polymer powder such as PMMA, polyvinylidene fluoride, polyimide, Teflon, and polyethylene, and the organic material may be a particle state or a carbon state.

The heat treatment of the pore-forming precursor powder is preferably carried out by calcining at 100 to 300 캜.

When the conductive oxide powder and the pore-forming precursor powder are mixed, the average particle size of the mixed powder mixed is 0.2 to 3 μm, preferably 0.5 to 2.0 μm, more preferably 0.7 to 1.5 μm, still more preferably 0.9 to 1.1 μm Adjust the average particle size by um.

The content of the pore precursor powder in the mixed powder is 10 to 60 vol%, preferably 10 to 50 vol%, more preferably 20 to 50 vol%, and still more preferably 30 to 50 vol% .

Here, the thickness of the anode diffusion preventing layer formed on the metal support is preferably 1 um to 30 um, preferably 2 to 10 um, more preferably 3 to 6 um.

Also, it is preferable that the anode diffusion preventive layer formed according to one embodiment of the present invention maintains the temperature of the fuel cell stack at 600 to 850 캜 for 2 hours or more during the initial operation raising of the fuel cell system. In this sintering process, the pore-forming precursor powder is also removed.

The metal support used in the method for manufacturing a fuel cell according to an embodiment of the present invention is preferably a ferritic stainless steel or an Fe-Cr alloy.

Wherein the metal support is used for any one of the Crofer22APU Crofer22H or ZMG232L, or the Fe-Cr alloy (Fe _100-x -Cr _x) (x = 16 ~ 30) and _{[Fe 74-y - 26Cr -} (Mo, Ti, Y 2 O 3) y (y = 0 ~ 5)], [Fe 100-xy - Cr x - M y] (x = 16 to 30 and y = 0 to 5) (M is any one of Ni, Ti, Ce, Mn, Mo, Co, La, Y and Al) in -Cr alloys 0 ~ 50 vol% of metal oxide _{(doped-Al 2 TiO 5,} doped-Zirconia, doped-Ceria, MgO, CaO, SrO, CoO x, ZnO, VO x, Cr 2 O 3, FeO, MoO _x , WO _x , Ga ₂ O ₃ , Al ₂ O ₃ , TiO ₂ and mixtures thereof).

In addition, the anode layer used in the method of manufacturing a cell for a fuel cell according to an embodiment of the present invention includes a composite of NiO and (ZrO ₂ ) _1-x (Y ₂ O ₃ ) _x (x = 0.08 to 0.1) ZrO ₂ ) _0.90 (Sc ₂ O ₃ ) _0.1-x (Yb ₂ O ₃ ) x (x = 0 to 0.06), NiO and Ce _1-x Ln _x O _2-δ , (Ln = Gd, Sm , Y, x = 0.1 to 0.3, ? = 0 to 0.2), or a mixture of these complexes.

The NiO content of the composite is preferably 40 to 75 wt%.

And the solid electrolyte layer used in the method of manufacturing the fuel cell according to one embodiment of the present invention is _{(ZrO 2) 1-x (} Y 2 O 3) x (x = 0.03 ~ 0.1), (ZrO 2) 0.89 ( (Sc ₂ O ₃ ) _0.1 (CeO ₂ ) _0.01 , (ZrO ₂ ) _0.90 (Sc ₂ O ₃ ) _0.1-x (Yb ₂ O ₃ ) _x (x = 0 to 0.06), Ce _1-x Ln _x O _{2- δ, (Ln = Gd, Sm} , Y, x = 0.1 ~ 0.3, δ = 0 ~ 0.2), and _{La 1-x Sr x Ga 1} -y Mg yz Co z O 3 ± δ (x = 0.1 ~ 0.3, y = 0.1 ~ 0.3, z = 0.01 ~ 0.15, δ = 0 ~ 0.2) , Or a mixture thereof.

In the meantime, the air electrode interface reaction preventing layer used in the method of manufacturing a fuel cell according to an embodiment of the present invention may be formed of Ce _1-x Ln _x O _{2 -δ} , where Ln = Gd, Sm, Y, x = δ = 0 to 0.2) based oxide.

The cathode layer used in the method for manufacturing a fuel cell according to an embodiment of the present invention is a composite in which an electric conductive oxide or a powder of the solid electrolyte composition is added in the range of 0 to 50 vol% desirable.

Wherein the electrically conductive oxide is selected from the group consisting of (Ln _1-x B _x ) _s MO ₃隆 (Ln = lanthanide or a mixture thereof, B = Ba, Sr, Ca, or a mixture thereof, M = Co, Fe, (A = La, Gd, Sm (x = 0.05 to 0.4, s = 0.9 to 1.0 and? = 0 to 0.3) and (A _1-x B _x ) _s Fe _{1 -y} Co _y O _3? X, y = 0 to 1.0, s = 0.9 to 1.0,? = 0 to 0.3) and (La1 _- xSr _x ) _s MnO _{3 ± δ} (x = 0.05 to 0.4, s = 0.9 to 1.0, ? = 0 to 0.3), or a mixture thereof.

The present invention can be applied to a fuel cell stack (Fuel Cell Stack) or a Fuel Cell Power Generation System (Fuel Cell Power Generation System) manufactured using the fuel cell manufactured by any one of the above- .

The cell of the metal support type solid oxide fuel cell according to the embodiment of the present invention has the technical effect of preventing the interface reaction between the metal support and the anode by forming the anode diffusion preventive layer made of the conductive oxide between the metal support and the anode have.

Also, since the cell of the metal support type solid oxide fuel cell according to the embodiment of the present invention is completed through the room temperature coating process without the high temperature sintering process, the sintering shrinkage does not occur, There is a technical effect that can be provided.

Also, since the anode diffusion preventing layer according to the present invention is excellent in the bonding force between the metal support and the oxide coating layer, there is a technical effect that coating of the oxide layer which can not be peeled off without surface treatment such as sand blasting, which causes warping in a thin metal thin plate, is possible.

Also, since the anode active material layer for a solid oxide fuel cell according to the present invention has a porous structure, the conductive oxide layer is first formed on a dense metal plate, and then the backside of the metal plate is removed If the holes are formed by etching, there is a technical effect that gas permeation through the porous oxide layer is possible.

The manufacturing yield of the fuel cell according to one embodiment of the present invention is high, and there is a technical effect that the warpage of the cell due to the difference in thermal expansion coefficient between the respective components can be minimized.

In addition, when the method of manufacturing a metal-supported type fuel cell according to one embodiment of the present invention, it is possible not only to achieve the technical effect of using an inexpensive metal scaffold, , And has a very excellent strength and flexibility.

Accordingly, when a fuel cell stack and a fuel cell power generation system are manufactured using a cell of a metal-supported solid oxide fuel cell manufactured according to an embodiment of the present invention, The battery stack or system has the technical effect of being resistant to thermal, mechanical shock and vibration and capable of rapid thermal cycling.

In addition, when the metal support type fuel cell having the anode diffusion preventing layer is used, thermal and mechanical reliability, which is a weak point of the conventional ceramic support type SOFC stack, can be improved in the power source fields of transportation equipment, mobile equipment, portable equipment, Commercialization of the battery can be expected.

FIG. 1 is a conceptual diagram showing an aerosol spraying apparatus used for manufacturing an anode diffusion preventing layer of a fuel cell according to an embodiment of the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The singular forms as used herein include plural forms as long as the phrases do not expressly express the opposite meaning thereto. Means that a particular feature, region, integer, step, operation, element and / or component is specified, and that other specific features, regions, integers, steps, operations, elements, components, and / And the like.

Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Commonly used predefined terms are further interpreted as having a meaning consistent with the relevant technical literature and the present disclosure, and are not to be construed as ideal or very formal meanings unless defined otherwise.

Hereinafter, embodiments of the present invention will be described in detail. These embodiments are only for illustrating the present invention, and the present invention is not limited thereto.

A method of manufacturing a cell of a metal-supported solid oxide fuel cell according to an embodiment of the present invention includes forming a fuel electrode diffusion preventing layer on a metal support, forming a fuel electrode layer thereon, forming a solid electrolyte layer on the fuel electrode layer, An air electrode interface preventing layer is selectively formed on the electrolyte layer, and a cathode layer is formed on the electrolyte layer in this order.

In order to manufacture a metal-supported solid oxide fuel cell according to an embodiment of the present invention, a metal support is first prepared.

The metal support is preferably a material having a small decrease in electrical conductivity due to high-temperature oxidation, a redox stability, and a thermal expansion coefficient of about 10 to 13 x 10 ^-6 / ^oC . The reason why the thermal expansion coefficient of the metal support is limited is to reduce the difference in thermal expansion coefficient between the metal support and each of the ceramic functional layers stacked thereon to prevent the separation of the functional layer or the warping of the cell due to the difference in thermal expansion coefficient between the respective components to be.

Ferrite-based stainless steel, Crofer22APU and Crofer22H from Tyssenkrupp, Germany, and ZMG232L from Hitachi Metal, Japan, are examples of materials for the metal support having such characteristics.

The Fe-Cr alloy includes (Fe _100-x -Cr _x ), and the Fe- (x = 16 ~ 30) and _{[Fe 74-y - 26Cr -} (Mo, Ti, Y 2 O 3) y (y = 0 ~ 5)], [Fe 100-xy - Cr x - M y] (x (M = Ni, Ti, Ce, Mn, Mo, Co, La, Y, or Al). In case of such an Fe-Cr alloy, 0 to 50 vol% of a metal oxide (doped-Al ₂ TiO ₅ , doped-zirconia, doped-ceria, MgO, CaO, SrO, CoO _x , ZnO, VO _x , Cr ₂ O ₃ , FeO, MoO _x , WO _x , Ga ₂ O ₃ , Al ₂ O ₃ , TiO _2, and mixtures thereof.

The thickness of the metal support is preferably in the range of 0.1 mm to 2 mm.

On the other hand, a ceramic powder to be used as an anode layer is prepared to form the anode layer. The composition of the ceramic powder forming the anode layer is a composite of NiO and (ZrO ₂ ) _{1 -x} (Y ₂ O ₃ ) _x (x = 0.08 to 0.1), NiO and (ZrO ₂ ) _0.90 (Sc ₂ O ₃ ) 0 . _{1-x (Yb 2 O 3} ) x (x = 0 ~ 0.06) of the composite, and NiO and _{Ce 1-x Ln x O 2} -δ, (Ln = Gd, Sm, Y, x = 0.1 ~ 0.3, ? = 0 to 0.2), or a mixture thereof.

More preferably, the anode layer ceramic powder is a composite of NiO and (ZrO ₂ ) _0.92 (Y ₂ O ₃ ) _0.08 solid electrolyte powder or a composite of NiO and Ce _0.9 Gd _0.1 O _{2 -δ} (δ = 0 to 0.2) solid electrolyte powder Can be used. Here, the content of NiO in such a composite is preferably in the range of 40 to 75 wt%. This is because NiO is reduced to Ni when the fuel cell is operated, and thus about 15 to 30% of pores are generated.

Nickel (NiO) in the anode layer reacts with components of the metal support, especially Fe, Cr, etc., during the operation of the fuel cell, thereby causing performance deterioration of the metal support type solid oxide fuel cell.

That is, when the nickel (Ni) component of the fuel electrode is diffused into the metal support composed of the ferritic stainless steel, the surface of the metal support is transformed into the austenitic stainless steel by the diffusion of nickel (Ni). Thus, the phase change when the ferritic stainless steel is that its thermal expansion coefficient is significantly increased from the original 10 ~ 12 x 10 ^-6 / ℃ to 18 ~ 20 x10 ^-6 / ℃.

When the thermal expansion coefficient of the metal support changes, the anode and the solid electrolyte having a thermal expansion coefficient in the range of 10 to 12 x 10 ^-6 / ° C may peel off. On the other hand, in the case of the Fe-Cr based metal support, when Fe and Cr components diffuse into the anode layer, the electrochemical activity of the anode layer is reduced, thereby deteriorating the performance of the cell.

The method of preventing the performance of the cell produced by the interfacial reaction between the metal support and the fuel electrode from being reduced is to form an anode diffusion preventive layer having electrical conductivity and gas permeation function without interfacial reaction with both the metal support and the anode .

This anode diffusion preventing layer has porosity and is formed on a metal support.

To this end, one embodiment of the present invention forms a mixture powder of a conductive oxide powder and a pore-forming precursor powder on a metal support by an aerosol spraying method to serve as an anode diffusion preventing layer.

The mixed powder for preventing the diffusion of the anode formed on the metal support by the aerosol spraying method is sprayed at a high speed toward the surface of the metal support in the state of the azole to have a strong binding force with the metal support even at room temperature and maintain the crystallinity of the aerosol constituent powder .

An anode diffusion preventive layer for a metal support type solid oxide fuel cell produced by an aerosol deposition method uses a mixture of a conductive oxide powder and a pore forming precursor powder.

The conductive oxides are selected from the group consisting of CeO ₂ , (La _1-x A _x ) Cr _1-y B _y O _{3 ± δ} (A = Sr, Ca or a mixture thereof x = 0.1 to 0.4; V, Fe, Ti, Ce, Ru or mixtures thereof, y = 0 ~ 0.5, δ = 0 ~ 0.3), (La 1-x A x) s Ti 1-y B y O 3 ± δ (A = Sr, Ca or a mixture thereof x = 0.1 to 0.6; B = Mn, Co, Cu, Ni, V, Fe, Ti, Ce, Ru or a mixture thereof, y = 0 to 0.5, s = 0.9 to 1.0, _{0.3), (Sr 1-x} A x) s Ti 1-y Nb y O 3 ± δ (A = y, La, Gd, Sm or mixtures thereof, x = 0.05 ~ 0.2; y = 0 ~ 0.5; s = 0.9 to 1.0, and? = 0 to 0.3).

The precursor powder for pore formation uses a material obtained by mixing one or more of polymer powder, organic particles and carbon particles.

As the polymer powder, PMMA, polyvinylidene fluoride, polyimide, Teflon, and polyethylene are preferable, and the organic material can be a particle state and a carbon particle state.

The mixed powder obtained by mixing the conductive oxide powder forming the anode diffusion preventing layer and the pore forming precursor powder is prepared by depositing the mixed powder on the metal support by the aerosol method and then removing the pore forming precursor powder during the cell manufacturing process, The pore-forming precursor is pyrolyzed, burned and removed at the step of raising the temperature of the fuel cell stack to the operating temperature of 600 to 850 ° C, which is the operating temperature of the stack, by manufacturing the solid oxide fuel cell, It is preferable that pores are formed.

Next, a method of forming an anode diffusion preventive layer on a metal support by using a mixed powder obtained by mixing a conductive oxide powder and a pore-forming precursor powder is described.

First, a conductive oxide powder is prepared, followed by heat treatment, followed by pulverizing it to adjust particle size. The precursor powder for pore formation to be mixed with the conductive oxide powder is prepared and heat-treated, followed by pulverizing and controlling the particle size.

The heat treatment of the prepared powder means that the conductive oxide powder and the pore-forming powder to be used are calcined. The calcining heat treatment is to remove moisture and impurities contained while controlling the size of powder particles to be used.

The heat treatment of the conductive oxide powder is performed at a temperature of 300 to 1200 ° C, preferably 600 to 1100 ° C, more preferably 800 to 1100 ° C, and further preferably 900 to 1000 ° C for the calcination heat treatment. The calcination temperature is 100 to 300 ° C.

The calcined conductive oxide powder and the pore-forming precursor powder are pulverized in a pulverizer and then pulverized in the order of 0.2 to 3 μm, preferably 0.5 to 2.0 μm, more preferably 0.7 to 1.5 μm, and even more preferably 0.9 to 1.1 μm To adjust the average particle size.

The prepared conductive oxide powder and the pore-forming precursor powder are mixed together to prepare a mixed powder. If the content of the pore forming precursor powder in the mixed powder is less than 10 vol%, the porosity is too low to form a gas passage for the cathode reaction. If the porosity is more than 60 vol% The content of the pore precursor is 10 to 60 vol%, preferably 10 to 50 vol%, more preferably 20 to 50 vol%, and still more preferably 30 to 50 vol%, since the electric conductivity is low and the strength of the film is low. %.

The prepared mixed powder is charged into an aerosol sprayer and then aerosol of the mixed powder is generated together with the transfer gas. Thereafter, the aerosol is sprayed at high speed onto the surface of the solid electrolyte substrate kept in a vacuum state to form the anode diffusion preventing layer.

At this time, the thickness of the anode diffusion preventing layer formed on the surface of the metal support substrate is preferably 1 um to 30 um, preferably 2 to 10 um, more preferably 3 to 6 um.

The anode diffusion preventive layer formed on the metal support substrate may be formed by directly coating the succeeding functional layer without sintering heat treatment, and then completing the fuel cell in this state. In the initial state of operating the fuel cell stack, pore formation Remove the precursor.

The following describes the process of removing the precursor for forming pores by taking the completed fuel cell as a metal-supported solid oxide fuel cell. For a metal-supported solid oxide fuel cell, its operating temperature is 600-850 ° C. At an initial operation at such an operating temperature, the pore forming precursor powder is oxidized and removed after more than 2 hours. When the pore-forming precursor is removed, pores formed continuously on the surface of the anode diffusion-preventing layer and the removed precursor site can be formed.

Among such pore-forming precursors, the polymer particles and the organic particles have a function of increasing the thickness of the anode diffusion preventing layer because they act to relax the stress in the anode diffusion preventing layer. For example, when polymer particles are not used, the stress of the layer may accumulate, resulting in a phenomenon that the layer is separated from the substrate after forming the layer in the case of the thick layer or during the heat treatment.

The thus formed anode diffusion preventing layer functions to suppress the interface reaction between the metal support and the anode in the fuel cell.

Therefore, when the anode diffusion preventing layer is formed, the reduction of the performance of the fuel cell cell during long-term operation at a high temperature is greatly reduced.

Next, referring to FIG. 1, a deposition method of coating an anode diffusion preventing layer on a metal support by an aerosol spraying method according to an embodiment of the present invention will be described.

As shown in FIG. 1, when the carrier gas is first delivered from the carrier gas storage chamber 10, the carrier gas is injected into the aerosol chamber 13 along the transfer pipe 11. As the carrier gas to be used at this time, an inert gas of any one of nitrogen, helium and argon may be used, or a mixed gas in which these gases are mixed with each other, or a mixed gas in which these gases are mixed with compressed air may be used.

A mixed powder prepared by mixing the prepared conductive oxide powder and the pore-forming precursor powder is injected into the air release chamber 13.

The carrier gas injected into the aerosol chamber 13 is transferred into the vacuum deposition chamber 15 together with the mixed powder powder in the chamber 13. [

At this time, the aerosol chamber 13 is vibrated vertically or horizontally by the vibration device 16. In this state, the carrier gas injected into the aerosol chamber 13 is mixed with the mixed powder to generate an aerosol.

On the other hand, the vacuum deposition chamber 15 is maintained in a vacuum state by a vacuum device 17. The vacuum device 17 is constituted by a booster pump and a rotary vacuum pump and the vacuum device 17 also functions to exhaust the transfer gas in the aerosol sucked into the vacuum deposition chamber 15. At this time, the degree of vacuum of the vacuum deposition chamber 15 is preferably maintained at 1 to 10 Torr. A pressure difference is generated between the aerosol chamber 13 and the vacuum deposition chamber 15 so that the aerosol formed in the aerosol chamber 13 is sucked into the vacuum deposition chamber 15 through the nozzle 19 toward the substrate 20 .

At this time, the distance between the nozzle 19 and the substrate 20 is preferably adjusted in the range of 1 to 20 mm. The slit through which the aerosol formed at the end of the nozzle 19 is discharged preferably has a width of 0.3 to 0.5 mm and a length of 10 to 40 mm.

However, the width and the length of the slit of the nozzle 19 can be selected as optimum conditions depending on the composition of the ceramic powder forming the aerosol and the state of the deposited layer to be deposited. In addition, the position of the nozzle and the position of the substrate can be changed from those shown in the drawings. It is possible to configure the apparatus such that the substrate is at the bottom, the nozzle is at the top, the substrate is fixed in a large area during the deposition process, the nozzle moves or the nozzle is fixed and the substrate moves.

The aerosol sprayed from the nozzle 19 onto the substrate 20 collides with the substrate 20 to deposit a dense ceramic film. As described above, the area of the ceramic film deposited on the substrate 20 can be controlled to a desired size while moving the nozzle to the left and right, and the thickness thereof can be controlled in proportion to the spraying time of the aerosol.

When the mixed powder in an aerosol state is injected at high speed toward the substrate 20 through the nozzle 19, the kinetic energy held by the mixed powder is transferred to the substrate 20. At this time, due to the impact of the mixed powder, the particles are finely pulverized and deformed at the same time to form new crystal grains. The crystal grains are deformed to minimize the surface area, and a high-density ceramic coating layer is formed.

When the mixed powder particles colliding with the substrate are repeatedly solidified by impact at room temperature, a dense coating layer having a desired thickness can be grown. Although the thus-formed coating layer is made finer, the crystalline nature of the raw material mixed powder is basically maintained, and a high-density film having excellent bonding force with the substrate is formed without further sintering process.

As described above, it is possible to manufacture a dense anode-electrode diffusion preventing layer having excellent bonding strength with a desired substrate without heat treatment.

When an anode diffusion preventing deposition layer is formed on a metal support substrate by an aerosol spraying method, the particle size of the mixed powder to be used has a great influence on the deposition layer formation. Therefore, in the embodiment of the present invention, the average particle diameter of the mixed powder to be deposited is limited to 0.2 to 3 μm. The average particle diameter of the preferred powder is 0.5 to 2.0 탆, more preferably 0.7 to 1.5 탆, and still more preferably 0.9 to 1.1 탆.

The reason why the average particle size of the mixed powder to be used is limited is that if the average particle size of the mixed powder is 0.2 μm or less, a dense film is not formed and a compressed powdery film is formed. If the average particle size is 3 μm or more, The coarse particles present in the coating layer sharply scrape off the substrate or coating layer, or the collision speed of the particles is insufficient to form a dense coating layer.

The particle size of the mixed powder is controlled through calcining heat treatment and crushing (for example, milling treatment) as described above. However, this control method is the same as the method for controlling the general ceramic particle diameter, and thus a detailed description thereof will be omitted.

As described above, the anode diffusion preventing layer is formed on the metal support, and then the anode is formed on the anode diffusion preventing layer. The method of forming the fuel electrode is the same as the method of forming the anode diffusion preventing layer, and the coating thickness of the anode layer is preferably 5 탆 to 30 탆 thick.

The following describes the process of depositing the solid electrolyte powder on the coated anode layer.

The ceramic powder used as a solid electrolyte layer _{(ZrO 2) 1-x (} Y 2 O 3) x (x = 0.03 ~ 0.1), (ZrO 2) 0.89 (Sc 2 O 3) 0.1 (CeO 2) 0.01, (ZrO ₂ ) _0.90 (Sc ₂ O ₃ ) _0.1-x (Yb ₂ O ₃ ) _x (x = 0 to 0.06), Ce _1-x Ln _x O _{2 -δ} , (Ln = Gd, Sm, ~ 0.3, δ = 0 ~ 0.2), and _{La 1-x Sr x Ga 1} -y Mg yz Co z O 3 ± δ (x = 0.1 ~ 0.3, y = 0.1 ~ 0.3, z = 0.01 ~ 0.15, δ = 0 ~ 0.2) , Or a mixture thereof is preferable.

The method of forming the solid electrolyte layer on the anode layer is the same as the method of forming the anode diffusion preventive layer, and thus a detailed description thereof will be omitted.

The coating thickness of the solid electrolyte layer formed on the anode layer is preferably 5 to 30 μm.

The following describes the process of depositing the air electrode interface reaction preventive layer on the coated solid electrolyte layer.

The air electrode interface reaction preventing layer may be selectively deposited on the upper portion of the solid electrolyte layer.

That is, when the solid electrolyte layer is a zirconia-based material, an interface reaction is caused between the material forming the air electrode, which will be described later, such as SrZrO ₃ and La ₂ Zr ₂ O ₇ An interface reaction layer having a high electrical resistance can be produced. Therefore, in order to prevent such an interfacial reaction, the air electrode interface reaction preventing layer is coated on the upper part of the solid electrolyte layer.

Zirconia based solid electrolytes _{(ZrO 2) 1-x (} Y 2 O 3) x (x = 0.03 ~ 0.1), (ZrO 2) 0.89 (Sc 2 O 3) 0.1 (CeO 2) 0.01 and (ZrO _{2) 0.90} (Sc ₂ O ₃ ) _0.1-x (Yb ₂ O ₃ ) _x (x = 0 to 0.06) ≪ / RTI > The interfacial reaction preventive layer coated on the zirconia-based solid electrolyte includes Ce _1-x Ln _x O _2-δ (Ln = Gd, Sm, Y, x = 0.1 to 0.3, δ = 0 to 0.2).

The method of forming the air electrode interface reaction preventing layer on the solid electrolyte layer is the same as the method of forming the above-described anode diffusion preventing layer, and thus a detailed description thereof will be omitted.

The thickness of the air electrode interface reaction preventive layer formed on the solid electrolyte layer is 1 um to 30 um, more preferably 2 to 6 um.

As described above, the fuel electrode diffusion preventing layer, the anode layer and the solid electrolyte layer, and optionally the air electrode interface reaction preventing layer are coated on the metal support, and then the air electrode layer is formed on the air electrode interface reaction preventing layer.

The cathode layer must be permeable to gas during operation of the fuel cell, so that its structure must be porous.

In the case of the anode layer, NiO is decomposed into Ni in the constituent powder during the operation of the fuel cell, resulting in pores ranging from 15 to 30%. Therefore, the anode layer functions even when it is coated by the aerosol spraying method. However, in the case of the cathode layer, it is difficult to form pores by self-decomposition of the material forming the cathode layer. Therefore, it is not preferable to coat the air electrode layer with the aerosol spray method.

Therefore, it is preferable that the cathode layer is formed by a paste or slurry of ceramic powder on the surface of the air electrode interface reaction prevention layer by a screen printing method or a spray coating method.

Thus, the cathode layer formed at room temperature is not heat-treated and the cell fabrication is completed. When the fuel cell system is directly operated after the air electrode layer is formed without heat treatment, the temperature of the fuel cell stack is maintained in the range of 600 to 850 ° C for at least 2 hours during the initial temperature raising process, thereby replacing the heat treatment.

The ceramic powder constituting the cathode layer is preferably a composite obtained by adding an electroconductive oxide or a powder of a solid electrolyte composition to the electroconductive oxide in a range of 0 to 50 vol%.

Wherein the electroconductive oxide includes at least _one of (Ln _1-x B _x ) _s MO ₃隆 (Ln = lanthanide or a mixture thereof, B = Ba, Sr, Ca, or a mixture thereof, M = Co, Fe, Mn, This mixture, x = 0.05 ~ 0.4, s = 0.9 ~ 1.0, δ = 0 ~ 0.3) and _{(A 1-x B x)} s Fe 1-y Co y O 3 ± δ (A = La, Gd, Sm, Pr, or a mixture thereof, B = Ba, Sr, Ca , or mixtures thereof, x = 0.05 ~ 0.4, y = 0 ~ 1.0, s = 0.9 ~ 1.0, δ = 0 ~ 0.3) , and (La _1-x Sr _x ) _s MnO _{3 ± δ} (x = 0.05 to 0.4, s = 0.9 to 1.0, ? = 0 to 0.3), or a mixture thereof.

As described above, the thickness of the air electrode layer formed on the air electrode interface reaction prevention layer is preferably from 10 μm to 50 μm.

While the invention has been shown and described with reference to certain exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the scope of the following claims. Those who do it will easily understand.

10; Carrier gas storage chamber
11; Conveying pipe
13; Aerosol chamber
15; Vacuum deposition chamber
16; Vibrating device
17; Vacuum device
19; Nozzle
20; Board

Claims (22)

delete A method of manufacturing a cell for a metal-supported solid oxide fuel cell includes:
Preparing the metal support;
Forming an anode diffusion preventing layer on one side of the metal support;
Forming an anode layer on the anode diffusion preventing layer;
Forming a solid electrolyte layer on the anode layer;
Selectively forming an air electrode interface reaction preventing layer on the solid electrolyte layer; And
And forming a cathode layer on the solid electrolyte layer or the air electrode interface reaction preventing layer,
Wherein the step of forming the anode diffusion preventing layer comprises forming a mixed powder of a conductive oxide powder and a pore forming precursor powder on a metal support by an aerosol spraying method. 3. The method of claim 2,
Wherein the forming of the fuel electrode layer, the solid electrolyte layer and the air electrode interface reaction preventing layer is performed by an aerosol spraying method. 3. The method of claim 2,
The step of forming the anode diffusion preventive layer by the aerosol spraying method comprises: preparing a powder by heat-treating and pulverizing a conductive oxide powder and a pore-forming powder; preparing powders by mixing the powders; A metal support type solid oxide fuel which forms an aerosol by injecting a transporting gas while applying mechanical vibration to the powder and then spraying the aerosol at high speed onto a metal support in a vacuum state to form an anode diffusion preventing layer by kinetic energy of the mixed powder; A method for manufacturing a battery cell. 3. The method of claim 2,
Wherein the conductive oxide powder is selected from the group consisting of CeO ₂ , (La _1-x A _x ) Cr _1-y B _y O _{3 隆} (A = Sr, Ca, (A _1-x A _x ) _s Ti _1-y B _y O _{3 隆} (A = 0, _{1, 2, 3,} Sr, Ca or a mixture thereof x = 0.1 to 0.6; B = Mn, Co, Cu, Ni, V, Fe, Ti, Ce, Ru or a mixture thereof; y = 0 to 0.5; s = 0.9 to 1.0; 0 to 0.3), (Sr _1-x A _x ) _s Ti _1-y Nb _y O _{3 隆} (A = Y, La, Gd, Sm or a mixture thereof, x = 0.05-0.2; y = s = 0.9 to 1.0, and? = 0 to 0.3). The method of manufacturing a cell for a metal-supported solid oxide fuel cell according to claim 1, 5. The method of claim 4,
Wherein the heat treatment of the conductive oxide powder is performed by calcining at a temperature of 300 to 1200 ° C. 3. The method of claim 2,
Wherein the pore-forming precursor powder is a mixture of at least one of PMMA, polyvinylidene fluoride, polyimide, Teflon, polyethylene, organic particles, and carbon particles or at least one of them. . 5. The method of claim 4,
Wherein the heat treatment of the pore-forming precursor powder is performed by calcining at 100 to 300 ° C. 3. The method of claim 2,
Wherein the mixed powder has an average particle diameter of 0.2 to 3 占 퐉. 3. The method of claim 2,
Wherein the mixed powder has an average particle diameter of 0.9um to 1.1um. 3. The method of claim 2,
Wherein the mixed powder has a pore-forming precursor powder content of 10 to 60 vol% in the total mixed powder. 3. The method of claim 2,
Wherein the thickness of the anode diffusion preventing layer formed on the metal support is 1 um to 30 um. 3. The method of claim 2,
The fuel electrode diffusion preventing layer formed in the step of forming the fuel electrode diffusion preventing layer is formed by holding the temperature of the fuel cell stack in the range of 600 to 850 캜 for 2 hours or more during the initial operation raising of the fuel cell system, Gt; 14. The method according to any one of claims 2 to 13,
Wherein the metal support is a ferritic stainless steel or an Fe-Cr alloy. 15. The method of claim 14,
The Fe-Cr alloy is (Fe _100-x -Cr _x ) (x = 16 ~ 30) and _{[Fe 74-y - 26Cr -} (Mo, Ti, Y 2 O 3) y (y = 0 ~ 5)], [Fe 100-xy - Cr x - M y] (x (M = Ni, Ti, Ce, Mn, Mo, Co, La, Y or Al) Cr-based alloy is doped with 0 to 50 vol% of a metal oxide (doped-Al ₂ TiO ₅ , doped-zirconia, doped-ceria, MgO, CaO, SrO, CoO _x , ZnO, VO _x , Wherein the mixture is a mixture of Cr ₂ O ₃ , FeO, MoO _x , WO _x , Ga ₂ O ₃ , Al ₂ O ₃ , TiO _2, and mixtures thereof. 14. The method according to any one of claims 2 to 13,
The fuel electrode layer is NiO and _{(ZrO 2) 1-x (} Y 2 O 3) x (x = 0.08 ~ 0.1) of the composite, NiO and _{(ZrO 2) 0.90 (Sc 2} O 3) 0.1-x (Yb 2 O ₃ ) x (x = 0 to 0.06), NiO and Ce _1-x Ln _x O _2-δ , (Ln = Gd, Sm, Y, lt; / RTI > = 0 to 0.2), or a mixture of these complexes. 17. The method of claim 16,
Wherein the NiO content of the composite is 40 to 75 wt%. 14. The method according to any one of claims 2 to 13,
The solid electrolyte layer _{(ZrO 2) 1-x (} Y 2 O 3) x (x = 0.03 ~ 0.1), (ZrO 2) 0.89 (Sc 2 O 3) 0.1 (CeO 2) 0.01, (ZrO 2) 0.90 (Sc ₂ O ₃ ) _0.1-x (Yb ₂ O ₃ ) _x (x = 0 to 0.06), Ce _1-x Ln _x O _{2 -δ} , (Ln = Gd, Sm, Y, δ = 0 ~ 0.2), and _{La 1-x Sr x Ga 1} -y Mg yz Co z O 3 ± δ (x = 0.1 ~ 0.3, y = 0.1 ~ 0.3, z = 0.01 ~ 0.15, δ = 0 ~ 0.2) Or a mixture thereof. The method of manufacturing a cell for a metal-supported solid oxide fuel cell according to claim 1, 14. The method according to any one of claims 2 to 13,
Wherein the air electrode interface reaction preventing layer is made of Ce _1-x Ln _x O ₂ -δ (Ln = Gd, Sm, Y, x = 0.1 to 0.3, lt; RTI ID = 0.0 ># = 0 ~ 0.2) < / RTI > 14. The method according to any one of claims 2 to 13,
(ZrO ₂ ) _1-x (Y ₂ O ₃ ) _x (x = 0.03 to 0.1), (ZrO ₂ ) _0.89 (Sc ₂ O ₃ ) _0.1 (CeO _{2 ) 0.01, (ZrO 2) 0.90} (Sc 2 O 3) 0.1-x (Yb 2 O 3) x (x = 0 ~ 0.06), Ce 1-x Ln x O 2-δ, (Ln = Gd, Sm, Y, x = 0.1 to 0.3, δ = 0 ~ 0.2), and _{La 1-x Sr x Ga 1} -y Mg yz Co z O 3 ± δ (x = 0.1 ~ 0.3, y = 0.1 ~ 0.3, z = 0.01 ~ 0.15, δ = 0 ~ 0.2) And a mixture thereof is added in a range of 0 to 50 vol%. The method of manufacturing a cell for a metal-supported solid oxide fuel cell according to claim 1, 21. The method of claim 20,
Wherein the electrically conductive oxide is selected from the group consisting of (Ln _1-x B _x ) _s MO ₃隆 (Ln = lanthanide or a mixture thereof, B = Ba, Sr, Ca or a mixture thereof, M = Co, Fe, Mn, This mixture, x = 0.05 ~ 0.4, s = 0.9 ~ 1.0, δ = 0 ~ 0.3) and _{(A 1-x B x)} s Fe 1-y Co y O 3 ± δ (A = La, Gd, Sm, Pr, or a mixture thereof, B = Ba, Sr, Ca , or mixtures thereof, x = 0.05 ~ 0.4, y = 0 ~ 1.0, s = 0.9 ~ 1.0, δ = 0 ~ 0.3) , and (La _1-x Sr _x ) _s MnO _{3 ± δ} (x = 0.05 to 0.4, s = 0.9 to 1.0, δ = 0 to 0.3), or a mixture thereof. The method of manufacturing a cell for a metal-supported solid oxide fuel cell according to claim 1, A fuel cell stack fabricated using the fuel cell produced by the method of any one of claims 2 to 13.

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